CN103962107B - A kind of preparation method of metal-modified humic acid defluorination absorbing material - Google Patents
A kind of preparation method of metal-modified humic acid defluorination absorbing material Download PDFInfo
- Publication number
- CN103962107B CN103962107B CN201410094157.5A CN201410094157A CN103962107B CN 103962107 B CN103962107 B CN 103962107B CN 201410094157 A CN201410094157 A CN 201410094157A CN 103962107 B CN103962107 B CN 103962107B
- Authority
- CN
- China
- Prior art keywords
- humic acid
- container
- preparation
- carry out
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011358 absorbing material Substances 0.000 title claims abstract 3
- 238000006115 defluorination reaction Methods 0.000 title claims abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004021 humic acid Substances 0.000 claims abstract description 22
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000010298 pulverizing process Methods 0.000 claims abstract 2
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 description 22
- 239000011737 fluorine Substances 0.000 description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 13
- -1 fluoride ions Chemical class 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003754 zirconium Chemical class 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种用腐植酸为原料制备除氟吸附材料的方法。 The invention relates to a method for preparing a fluorine-removing adsorption material by using humic acid as a raw material.
背景技术 Background technique
氟是重要的化工原料，氟及相关氟化物广泛应用于焦炭、玻璃、化肥、电镀、电子、农药、太阳能电池等行业。在氟化物的生产和应用过程中会产生大量的高浓度含氟废水，造成了环境污染。氟污染日益受到人们的关注,若处理不当，会对人体健康和水环境安全造成严重危害。为了保护人类的生存环境，提高人们的生活质量，含氟废水的除氟研究是国内外环保及卫生领域的重要任务。 Fluorine is an important chemical raw material. Fluorine and related fluorides are widely used in coke, glass, fertilizer, electroplating, electronics, pesticides, solar cells and other industries. During the production and application of fluoride, a large amount of high-concentration fluorine-containing wastewater will be generated, causing environmental pollution. Fluorine pollution has drawn more and more people's attention. If it is not handled properly, it will cause serious harm to human health and water environment safety. In order to protect the living environment of human beings and improve people's quality of life, the research on defluoridation of fluorine-containing wastewater is an important task in the field of environmental protection and hygiene at home and abroad.
国内外目前处理含氟工业废水的方法有多种，包括电凝聚、化学沉降、反渗析、离子交换、混凝沉淀和吸附等方法。由于吸附法具有运用成本低、工艺简单、除氟效果好等突出优点，因而被广泛应用于低浓度含氟废水的处理；即使是高浓度含氟工业废水，为确保出水达标，在处理时往往需要用吸附作为深度处理单元。 There are many methods for treating fluorine-containing industrial wastewater at home and abroad, including electrocoagulation, chemical precipitation, reverse osmosis, ion exchange, coagulation precipitation and adsorption. Because the adsorption method has outstanding advantages such as low operating cost, simple process, and good fluoride removal effect, it is widely used in the treatment of low-concentration fluorine-containing wastewater; Adsorption is required as an advanced treatment unit.
吸附法成功应用的关键是选择适宜的吸附材料。开发新型、高效、廉价的除氟吸附材料以降低水处理成本成为材料科学和环境科学领域里的重要研究课题。根据所用的原料，可将除氟吸附材料分为稀土吸附材料、含铝吸附材料、天然高分子吸附材料及其它吸附材料。在这些不同的除氟吸附材料中，天然有机高分子吸附材料因来源广泛、比表面积大、环境友好正受到越来越多的关注，但其机械强度低，对氟的选择性较差。将一些与氟具有较高亲和力的无机金属离子以某种方式负载到天然有机高分子上所获得的材料不仅具有较高的机械强度，而且还具有吸附容量大、吸附选择性高的优点，在去除水中氟离子时具有很强的竞争优势。 The key to the successful application of adsorption method is to choose the appropriate adsorption material. It has become an important research topic in the fields of material science and environmental science to develop new, efficient and cheap fluorine removal adsorption materials to reduce the cost of water treatment. According to the raw materials used, the fluorine removal adsorption materials can be divided into rare earth adsorption materials, aluminum-containing adsorption materials, natural polymer adsorption materials and other adsorption materials. Among these different adsorption materials for fluorine removal, natural organic polymer adsorption materials are attracting more and more attention due to their extensive sources, large specific surface area, and environmental friendliness, but their mechanical strength is low and their selectivity to fluorine is poor. The materials obtained by loading some inorganic metal ions with high affinity with fluorine onto natural organic polymers in a certain way not only have high mechanical strength, but also have the advantages of large adsorption capacity and high adsorption selectivity. It has a strong competitive advantage when removing fluoride ions in water.
腐植酸是自然界广泛存在的有机高分子物质， 它具有胶体的性质和疏松的“海绵状”结构，使其产生巨大的表面积和表面能。腐植酸分子中含有羟基、羧基等活性基团，可与水中金属离子发生离子交换、络合反应及表面吸附作用，也与电负性较强的物质发生氢键吸附作用。此外，在pH降低或外加电解质条件下腐植酸易产生胶凝。通过上述作用，可使腐植酸与加入的金属离子复合，所形成的复合物将赋予腐植酸新的功能，从而可以根据不同需要制备成各种有特殊功能的复合材料。因此，将与氟具有亲和力的金属化合物与腐植酸复合，制备成一种新型吸附材料，可体现出来源广、价格低廉、选择性高、除氟效率高等优点，开发这类新型除氟吸附材料具有较大实用价值。 Humic acid is an organic polymer substance that exists widely in nature. It has colloidal properties and a loose "sponge-like" structure, which makes it produce a huge surface area and surface energy. Humic acid molecules contain hydroxyl, carboxyl and other active groups, which can undergo ion exchange, complexation reaction and surface adsorption with metal ions in water, and hydrogen bond adsorption with substances with strong electronegativity. In addition, humic acid is prone to gelation when the pH is lowered or the electrolyte is added. Through the above functions, the humic acid can be compounded with the added metal ions, and the formed complex will endow the humic acid with new functions, so that various composite materials with special functions can be prepared according to different needs. Therefore, a new type of adsorption material is prepared by compounding a metal compound with an affinity with fluorine and humic acid, which can reflect the advantages of wide source, low price, high selectivity, and high fluoride removal efficiency. Great practical value.
发明内容 Contents of the invention
本发明的目的在于提供一种原料来源广、制备工艺简单、除氟效率高、成本低廉的除氟吸附材料及其制备方法。 The object of the present invention is to provide a fluoride removal adsorption material with wide source of raw materials, simple preparation process, high fluoride removal efficiency and low cost and a preparation method thereof.
本发明的特征在于用氢氧化钠和水将腐植酸配制成腐植酸钠溶液，将硝酸铝和硝酸氧锆溶解于耐酸碱的容器中，在剧烈搅拌下将所配制的腐植酸钠溶液加入到该容器中，用氢氧化钠和硝酸调节容器中混合溶液的pH值至设定值，进行物料的聚合反应，聚合反应结束后，进行固液分离，将固体进行洗涤、冷冻干燥并粉碎得到所需吸附材料，硝酸铝与腐植酸的质量比为1:1～1:2，硝酸氧锆与腐植酸的质量比为1:5～1:10，搅拌速度为120～250r/min，整个聚合反应过程的温度为50～70℃，混合溶液的pH值为6～8，物料聚合的时间为30～90min，冷冻干燥的冷阱温度为-40～-60℃，冷冻干燥的真空度为1～10Pa, 冷冻干燥的时间为12～24h。 The present invention is characterized in that humic acid is formulated into sodium humate solution with sodium hydroxide and water, aluminum nitrate and zirconium oxynitrate are dissolved in an acid and alkali resistant container, and the prepared sodium humate solution is added to into the container, use sodium hydroxide and nitric acid to adjust the pH value of the mixed solution in the container to the set value, and carry out the polymerization reaction of the material. After the polymerization reaction is completed, carry out solid-liquid separation, wash the solid, freeze-dry and pulverize to obtain The required adsorption material, the mass ratio of aluminum nitrate and humic acid is 1:1～1:2, the mass ratio of zirconium oxynitrate and humic acid is 1:5～1:10, the stirring speed is 120～250r/min, the whole The temperature of the polymerization reaction process is 50-70°C, the pH value of the mixed solution is 6-8, the time for material polymerization is 30-90min, the temperature of the freeze-drying cold trap is -40--60°C, and the vacuum degree of freeze-drying is 1～10Pa, freeze-drying time is 12～24h.
本发明的目的是这样实现的：腐植酸在氢氧化钠/水作用下可形成pH较高的溶液，当将该溶液加入到pH较低的铝盐和锆盐溶液中时，溶液中除了发生腐植酸和金属离子的络合反应外，还同时发生铝盐和锆盐的水解、缩聚反应和腐植酸的胶凝作用。铝盐和锆盐水解时产生的质子不断与腐植酸分子上的羧基、羟基、氨基结合，促进铝盐和锆盐水解聚合，同时，也加剧了腐植酸的胶凝。铝盐和锆盐的水解缩聚产物与胶凝的腐植酸共同聚集，在一定的条件下生成腐植酸-Al2O3-ZrO2水凝胶聚合物。经过固液分离和洗涤过程，可使水凝胶聚合物中的杂质减少，提高凝胶聚合物的纯度。在冷冻干燥过程中，水凝胶聚合物中的水分进一步脱去，形成三维的具有网状结构的腐植酸-Al2O3-ZrO2气凝胶复合体。通过干燥过程，材料的机械强度进一步增强，材料结构进一步加固。 The purpose of the present invention is achieved in that humic acid can form a solution with a higher pH under the action of sodium hydroxide/water, and when the solution is added to the lower aluminum salt and zirconium salt solution of pH, in the solution, in addition to In addition to the complex reaction of humic acid and metal ions, hydrolysis of aluminum salt and zirconium salt, polycondensation reaction and gelation of humic acid also occur simultaneously. The protons generated during the hydrolysis of aluminum salt and zirconium salt continue to combine with carboxyl, hydroxyl, and amino groups on humic acid molecules to promote the hydrolysis polymerization of aluminum salt and zirconium salt, and at the same time, it also intensifies the gelation of humic acid. The hydrolyzed polycondensation products of aluminum salt and zirconium salt aggregate together with gelled humic acid to generate humic acid-Al 2 O 3 -ZrO 2 hydrogel polymer under certain conditions. Through the process of solid-liquid separation and washing, the impurities in the hydrogel polymer can be reduced, and the purity of the gel polymer can be improved. During the freeze-drying process, the moisture in the hydrogel polymer is further removed to form a three-dimensional humic acid-Al 2 O 3 -ZrO 2 airgel complex with a network structure. Through the drying process, the mechanical strength of the material is further enhanced and the structure of the material is further strengthened.
在冷冻干燥水凝胶聚合物的过程中，水凝胶聚合物被预先降温冻结成固体，然后在真空的条件下使水蒸汽直接升华出来，而固体成份被在其位置上的坚冰支持着，留下大量孔隙，这会使得干燥后的产品疏松多孔，呈海绵状。因此，通过上述方法制得的吸附材料既具有较高的孔隙率和巨大的比表面积可对水中氟离子进行表面吸附，又含有大量的羟基，羧基，氨基可对水中氟离子进行氢键吸附，材料中还含有大量的对氟具有高度亲和力的铝和锆，可对水中氟离子进行化学吸附，提高了吸附材料对氟的吸附容量和选择性。 In the process of freeze-drying the hydrogel polymer, the hydrogel polymer is pre-cooled and frozen into a solid, and then the water vapor is directly sublimated under vacuum conditions, and the solid component is supported by the ice in its position , leaving a large number of pores, which will make the dried product loose and porous, with a spongy appearance. Therefore, the adsorption material prepared by the above method not only has a high porosity and a huge specific surface area for surface adsorption of fluoride ions in water, but also contains a large number of hydroxyl groups, carboxyl groups, and amino groups for hydrogen bond adsorption of fluoride ions in water. The material also contains a large amount of aluminum and zirconium with high affinity for fluorine, which can chemically adsorb fluorine ions in water, improving the adsorption capacity and selectivity of the adsorption material for fluorine.
相对于现有方法，本发明的突出优点是采用了环境友好、来源广泛、价格低廉的有机高分子物质为原料；制备工艺简单，制备条件容易控制；制备的成品既具有较高的孔隙率和比表面积，又含有对氟具有高度亲和力的活性组分，对水中氟离子的吸附效率高，具有明显的经济效益和环境效益。 Compared with the existing method, the outstanding advantages of the present invention are that the organic macromolecular substances that are environmentally friendly, widely sourced, and cheap are used as raw materials; the preparation process is simple, and the preparation conditions are easy to control; the prepared finished product has both high porosity and The specific surface area also contains active components with a high affinity for fluorine, which has a high adsorption efficiency for fluoride ions in water, and has obvious economic and environmental benefits.
具体实施方法Specific implementation method
实施例1: 用氢氧化钠和去离子水将10g腐植酸配制成0.2L 、pH=13的腐植酸钠溶液。在0.5L反应釜中，加入10g硝酸铝粉末和1g硝酸氧锆粉末，加入0.1L去离子水溶解，在反应温度为65~70℃和搅拌（搅拌速度220r/min）的条件下加入0.2L所配制的腐植酸钠溶液，用氢氧化钠和硝酸调节混合溶液的pH为7.5~7.8，在65~70℃下搅拌（搅拌速度220r/min）30 min，冷却至室温，离心分离，用0.5L去离子水洗涤3次，将离心所得固体放入真空冷冻干燥机中，在冷阱温度为-60℃，真空度为1Pa的条件下干燥24h，干燥后产物经研磨，制得金属改性腐植酸除氟吸附材料。在废水pH为7，水温20℃，投加量为5g/L，吸附时间为6h的条件下用该吸附材料处理氟离子初始浓度为22.55mg/L的含氟废水时，氟离子去除效率高达98.64%，吸附量大于4.45mg/g；在该条件下处理氟离子初始浓度为290mg/L的含氟废水时，氟离子去除效率高达95.06%，吸附量大于55.14mg/g。 Example 1: Prepare 10 g of humic acid with sodium hydroxide and deionized water to prepare 0.2 L of sodium humate solution with pH=13. In a 0.5L reactor, add 10g of aluminum nitrate powder and 1g of zirconyl nitrate powder, add 0.1L of deionized water to dissolve, and add 0.2L of For the prepared sodium humate solution, use sodium hydroxide and nitric acid to adjust the pH of the mixed solution to 7.5~7.8, stir at 65~70°C (stirring speed 220r/min) for 30 min, cool to room temperature, centrifuge, and use 0.5 Wash with L deionized water for 3 times, put the centrifuged solid into a vacuum freeze dryer, and dry it for 24 hours at a cold trap temperature of -60°C and a vacuum of 1 Pa. After drying, the product is ground to obtain a metal-modified Humic acid defluoridation adsorption material. When the pH of the wastewater is 7, the water temperature is 20°C, the dosage is 5g/L, and the adsorption time is 6h, when the adsorption material is used to treat fluorine-containing wastewater with an initial concentration of fluoride ions of 22.55mg/L, the removal efficiency of fluoride ions is as high as 98.64%, and the adsorption capacity is greater than 4.45mg/g; under these conditions, when treating fluorine-containing wastewater with an initial concentration of fluoride ions of 290mg/L, the fluoride ion removal efficiency is as high as 95.06%, and the adsorption capacity is greater than 55.14mg/g.
实施例2：用氢氧化钠和去离子水将40g腐植酸配成0.8L、 pH=13的腐植酸钠溶液。在2L的反应釜中，加入20g硝酸铝和8g硝酸氧锆粉末，加0.4L去离子水溶解，在反应温度为50~55℃和搅拌（搅拌速度150r/min）的条件下加入0.8L所配制的腐植酸钠溶液，用氢氧化钠和硝酸调节混合溶液pH为6.5~6.7，继续在50~55℃下搅拌（搅拌速度150r/min）90 min，冷却至室温，离心分离，用1L去离子水洗涤3次，将离心所得固体放入真空冷冻干燥机中，在冷阱温度为-45℃，真空度为5Pa的条件下干燥12h，干燥后产物经研磨，制得金属改性腐植酸除氟吸附材料。在废水pH为7，水温20℃，投加量为5g/L，吸附时间为6h的条件下用该吸附材料处理氟离子初始浓度为22.55mg/L的含氟废水时，氟离子去除效率高达97.89%，吸附量大于4.42mg/g；在该条件下处理氟离子初始浓度为290mg/L的含氟废水时，氟离子去除效率高达91.52%，吸附量大于53.08mg/g。 Example 2: 40 g of humic acid was formulated with sodium hydroxide and deionized water into a 0.8 L, pH=13 sodium humate solution. In a 2L reaction kettle, add 20g of aluminum nitrate and 8g of zirconium oxynitrate powder, add 0.4L of deionized water to dissolve, and add 0.8L of the For the prepared sodium humate solution, use sodium hydroxide and nitric acid to adjust the pH of the mixed solution to 6.5~6.7, continue to stir at 50~55°C (stirring speed 150r/min) for 90 min, cool to room temperature, centrifuge, and use 1L to remove Wash with ionic water for 3 times, put the solid obtained by centrifugation into a vacuum freeze dryer, dry for 12 hours at a cold trap temperature of -45°C, and a vacuum of 5 Pa, and grind the dried product to obtain metal-modified humic acid Fluorine removal adsorption material. When the pH of the wastewater is 7, the water temperature is 20°C, the dosage is 5g/L, and the adsorption time is 6h, when the adsorption material is used to treat fluorine-containing wastewater with an initial concentration of fluoride ions of 22.55mg/L, the removal efficiency of fluoride ions is as high as 97.89%, and the adsorption capacity is greater than 4.42mg/g; under these conditions, when treating fluorine-containing wastewater with an initial concentration of fluoride ions of 290mg/L, the fluoride ion removal efficiency is as high as 91.52%, and the adsorption capacity is greater than 53.08mg/g.
Claims (1)
- null1. the preparation method of a metal-modified humic acid defluorination absorbing material，It is characterized in that, with NaOH and water, humic acid is configured to sodium humate solution，Aluminum nitrate and zirconyl nitrate are dissolved in the container of acid and alkali-resistance，With vigorous stirring the sodium humate solution prepared is joined in this container，By the pH value of mixed solution in NaOH and nitric acid regulation container to setting value，Carry out the polymerisation of material，After polymerisation terminates，Carry out separation of solid and liquid，Solid is washed、Freeze-drying pulverizing obtain required sorbing material，Aluminum nitrate is 1:1～1:2 with the mass ratio of humic acid，Zirconyl nitrate is 1:5～1:10 with the mass ratio of humic acid，Mixing speed is 120～250r/min，The temperature of whole polymerization process is 50～70 DEG C，The pH value of mixed solution is 6～8，The time of material polymerization is 30～90min，Cryodesiccated condenser temperature is-40～-60 DEG C，Cryodesiccated vacuum is 1～10Pa,The cryodesiccated time is 12～24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410094157.5A CN103962107B (en) | 2014-03-14 | 2014-03-14 | A kind of preparation method of metal-modified humic acid defluorination absorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410094157.5A CN103962107B (en) | 2014-03-14 | 2014-03-14 | A kind of preparation method of metal-modified humic acid defluorination absorbing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103962107A CN103962107A (en) | 2014-08-06 |
| CN103962107B true CN103962107B (en) | 2016-08-24 |
Family
ID=51232395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410094157.5A Expired - Fee Related CN103962107B (en) | 2014-03-14 | 2014-03-14 | A kind of preparation method of metal-modified humic acid defluorination absorbing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103962107B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096547B (en) * | 2014-08-10 | 2017-11-28 | 锦洋高新材料股份有限公司 | A kind of efficiently humic acid fluorine ion absorber |
| CN113122529B (en) * | 2019-12-31 | 2023-01-10 | 中国石油化工股份有限公司 | Microorganism immobilization material and preparation method and application thereof |
| CN112121773A (en) * | 2020-09-27 | 2020-12-25 | 南通大学 | A kind of biological adsorption material for fluorine removal and preparation method thereof |
| CN112121772A (en) * | 2020-09-27 | 2020-12-25 | 南通大学 | Defluorination wood film filtering device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102814169A (en) * | 2012-09-21 | 2012-12-12 | 河南省科学院化学研究所有限公司 | Fluorine-removing lanthanum-supported fiber adsorbent and synthesis method thereof |
| CN103506088A (en) * | 2013-10-16 | 2014-01-15 | 四川师范大学 | Method for preparing defluorination absorption material by using sodium humate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5779934B2 (en) * | 2011-03-25 | 2015-09-16 | 栗田工業株式会社 | Calcium fluoride recovery method |
-
2014
- 2014-03-14 CN CN201410094157.5A patent/CN103962107B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102814169A (en) * | 2012-09-21 | 2012-12-12 | 河南省科学院化学研究所有限公司 | Fluorine-removing lanthanum-supported fiber adsorbent and synthesis method thereof |
| CN103506088A (en) * | 2013-10-16 | 2014-01-15 | 四川师范大学 | Method for preparing defluorination absorption material by using sodium humate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103962107A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105381782B (en) | One kind going ammonia nitrogen and phosphatic modified zeolite adsorbent and its preparation and regeneration method in water removal | |
| CN104289179B (en) | Method for preparing attapulgite/carbon composite adsorbent by one-step carbonization-activation | |
| CN103877953B (en) | A kind of hydrogel for sewage disposal and preparation method thereof | |
| CN103962107B (en) | A kind of preparation method of metal-modified humic acid defluorination absorbing material | |
| CN105289562B (en) | Heavy metal wastewater thereby recoverying and utilizing method | |
| CN106140113A (en) | A kind of graphene oxide/polymer gel and its preparation method and application | |
| CN108187641B (en) | Preparation method and application of a sodium alginate/polyvinyl alcohol@polyacrylamide core-shell structure gel ball | |
| CN103880008B (en) | A kind of method of utilizing ultrasonic wave to prepare active carbon | |
| CN104289178B (en) | The method preparing attapulgite/carbon adsorbent based on hydro-thermal-activation coupling technology | |
| CN104492391B (en) | A kind of preparation method of chitosan-modified albumin nanospheres heavy-metal adsorption material | |
| CN107185546A (en) | A kind of bismuth ferrite graphene oxide composite material preparation method | |
| CN103466771A (en) | Method for preparing oxidized form polysilicic acid ferro-aluminum coagulant | |
| CN104163463A (en) | Method for adsorbing heavy metal ions in solution by virtue of silk fibroin | |
| CN102921385B (en) | Process for preparing modified humic acid fluorine-removal adsorption material | |
| CN105148869B (en) | A kind of preparation method and application of chitosan calcium adsorption particle | |
| CN106672957A (en) | Method for preparing graphene oxide according to Fenton oxidation method | |
| CN109482146A (en) | A kind of preparation method of modified sewage sludge absorbent charcoal heavy-metal adsorption material | |
| CN109231758A (en) | A kind of modified sewage sludge absorbent charcoal heavy-metal adsorption material | |
| CN106824066B (en) | Modified zirconium hydroxide composite adsorbing material of the 3D graphene of fluorine ion and preparation method thereof in a kind of removal rural potable water | |
| CN104475021A (en) | Nitrogen-rich tea seed shell activated carbon as well as preparation method and application thereof | |
| CN103506088B (en) | A kind of method using sodium humate to prepare defluoride adsorption material | |
| CN102989422A (en) | Composite absorption material capable of removing phosphate radical in water as well as preparation method thereof | |
| CN103949221B (en) | A kind of synthetic method of the Chitosan-crown Ethers material for adsorption uranium | |
| CN103274402A (en) | Method for preparing active carbon by using polyving akohol | |
| CN103556455B (en) | Preparation method of polyphenylene sulfide based strong acid ion exchange fiber with high exchange capacity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20170314 |